Highly Stable Zinc-Based Metal-Organic Frameworks and Corresponding Flexible Composites for Removal and Detection of Antibiotics in Water.

Abstract

Antibiotic contamination of water bodies is a major environmental concern. Exposure to superfluous antibiotics is an ecological stressor correlated to the development of antibiotic resistance. Thus, it is imperative that effective methods are developed to simultaneously detect and remove such antibiotics so as to avoid inadvertent release. Herein, two flexible three-dimensional (3D) zinc-based metal-organic frameworks (MOFs) {[Zn2(bcob)(OH)(H2O)]·DMA}n (ROD-Zn1) and {[Zn(Hbcob)]·(solvent)}n (ROD-Zn2) (H3bcob = 1,3-bis((4'-carboxylbenzyl)oxy)benzoic acid) with rod second building units (SBUs) are successfully prepared. Their exceptional water and chemical stabilities (toward both acid and base), fast sorption kinetics, and unique framework endow the MOFs with excellent uptake capacity toward various antibiotics in the aqueous environment. The adsorption performance was further optimized by one-pot preparation of MOF-melamine foam (MF) hybrid composites, resulting in a hierarchical microporous-macroporous MOF@MF system (ROD-Zn1@MF and ROD-Zn2@MF), which are readily recyclable after adsorptive capture. The mechanisms of adsorption have been deeply investigated by static and competitive adsorption experiments. In addition, the MOFs exhibit excellent fluorescent properties and quenched by trace amounts of antibiotics in water solution. Therefore, ROD-Zn1 and ROD-Zn2 present a dual-functional performance, being promising candidates for detection and removal of antibiotics.